Application of 204mPb Perturbed Angular Correlation of 纬-rays Spectroscopy in Coordination Chemistry

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• 作者：Johan Vibenholt ; Magnus Schau-Magnussen ; Monika Stachura ; Morten J. Bjerrum ; Peter W. Thulstrup ; Vaida Arcisauskaite ; Lars Hemmingsen
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：February 20, 2012
• 年：2012
• 卷：51
• 期：4
• 页码：1992-1994
• 全文大小：209K
• 年卷期：v.51,no.4(February 20, 2012)
• ISSN：1520-510X

文摘

^204mPb perturbed angular correlation of 纬-rays (PAC) spectroscopy has been applied successfully for the first time to detect the nuclear quadrupole interaction in a lead(II) coordination compound in a molecular crystal [tetraphenylarsonium lead(II) isomaleonitriledithiolate ([AsPh₄]₄[Pb₂(i-mnt)₄])]. The recorded parameters from a powder crystalline sample are 谓_Q = 0.178(1) GHz and 畏 = 0.970(7). The electric field gradient (EFG) was determined at the PW91/QZ4P level including relativistic effects using the two-component zeroth-order regular approximation method for both the [Pb(i-mnt)₂]^{2鈥?/sup> monomer and the [Pb₂(i-mnt)₄]4鈥?/sup> dimer. Only the EFG for the latter compares favorably with the experimental data, indicating that the picture of this complex as a prototypical hemidirected coordination geometry with a stereochemically active lone pair on lead(II) is inadequate. Advantages and limitations of 204mPb PAC spectroscopy as a novel technique to elucidate the electronic and molecular structures of lead-containing complexes and biomolecules are presented.}